Manufacturing of Important

Polymers

CHAPTER 3-1
 E R
S T
Y E
O L
P
 Introduction

 Polyesters form a large class of commercially important polymers.

 A typical polyester is poly(ethylene terephthalate) (PET), the largest
volume synthetic fiber.
 The monomer of polyester (PET) is:-
 dimethyl terephthalate and
 ethylene glycol.
 Cont’d
 The term 'polyester' is, however, a specific chemical name which refers to any
polymer in which the linkage of small molecules takes place through the
formation of ester groups.

 polyester fibres are subdivided into the following types, based upon their
chemical structures:-

1) Polyethylene Terephthalate Fibres (PET).

2) Poly-1,4-Cyclohexylene-Dimethylene Terephthalate (PCDT).

3) Other types of polyester fibres.
 Cont’d
 The traditional route for the production of commercial PET is through
two successive ester interchange reactions.
1) DMT [dimethyl terephthalate] route: Raw materials are dimethyl
terephthalate (DMT) and monoethylene glycol (MEG)
2) PTA [purified terephthalic acid] route: Raw materials are
terephthalic acid (TPA) and monoethylene glycol (MEG).
 Cont..
1. DMT [dimethyl terephthalate] route:

Diglycol
Terephthalate
(DGT)
Methanol
Methanol

ethylene glycol.
Transesterfication
 Cont..
2. PTA [purified terephthalic acid] route:

Direct esterification
 Cont..
 A high molecular weight PET is an essential prerequisite for fiber
formation.
 To obtain high molecular weight PET, it is imperative that the two
monomers are present in equimolar (1:1) proportion during reaction.
 Otherwise the resultant product will be of low molecular weight.
 To ensure this stoichiometry ratio of 1:1, an intermediate reaction is
conducted between the two monomers (DMT and MEG or TPA and MEG)
to produce a new intermediate, diglycol terephthalate (DGT).
 Cont..
 In the first step, a 1:2 molar ratio of dimethyl terephthalate to ethylene glycol
is heated at temperatures near 200°C in the presence of a catalyst such as
calcium acetate.
 During this stage, methanol is evolved and an oligomeric product (x = 1 to 4)
is obtained.
 The second step involves a temperature increase to about 300°C.
 This results in the formation of high polymer with the evolution of ethylene
glycol.
POLYAMIDES
 Nylon 6
 Nylon6, 6
 Cont..
 Polyamides are polymers which contain repeating amide, -CONH-, linkages on
the polymer main chain.
 Theoretically, a large number of polyamides can be synthesized based on four main
synthetic routes:

(1) condensation reaction between a dicarboxylic acid and a diamine,

(2) reaction between a diacid chloride and a diamine,

(3) dehydration–condensation reactions of amino acids, and

(4) ring-opening polymerization of lactams.

 Cont..
 Nylon is a manufactured fiber in which fiber-forming substance is a
long-chain synthetic polyamide in which less than 85 % of the amide
linkages are attached directly to two aromatic rings.
 A polyamide in which at least 85 % of the amide links are joined to two
aromatic groups is known as an ‘aramid.’ (e.g. Kevlar)

Simple aromatic ring

 Nylon Polymer Production
 Nylon is a thermoplastic silky material, first used commercially in a

nylon-bristled toothbrush (1938), followed more famously by women's

stockings.

 It is made of repeating units linked by amide bonds and is frequently

referred to as polyamide (PA).

 Nylon was the first commercially successful synthetic polymer.

 Cont..
 In making nylon for fiber applications, the molecules with an acid

(COOH) group on each end are reacted with molecules containing

amine (NH2) groups on each end.

 The resulting nylon is named on the basis of the number of carbon

atoms separating the two acid groups and the two amines.

 These are formed into monomers of intermediate molecular weight,

which are then reacted to form long polymer chains.

 Nylon 6 synthesis
 Caprolactam is the starting material (monomer) for Nylon 6 polymerization.
 Caprolactam can be produced from three hydrocarbon feed stocks: cyclohexane,
phenol, and toluene.
 Both nylon6 and nylon6, 6 are manufactured from benzene via cyclohexane.
 Hydrogen is passed through liquid benzene in the presence of a nickel catalyst
under pressure:
 Cont..
 Cyclohexane is oxidized by passing air through the liquid under pressure in the
presence of a catalyst (often a cobalt salt) to yield two products:

 The mixture of cyclohexanol and cyclohexanone is known as "mixed oil" or KA

(ketone/alcohol).
 Cont..
 To make polyamide 6, pure cyclohexanone is required.
 When the mixed oil is heated under pressure with copper(ll) and
chromium(lll) oxides, the cyclohexanol, which is a secondary alcohol,
is dehydrogenated to the corresponding ketone, cyclohexanone:
 Cont..
 Cyclohexanone is then converted into caprolactam via the oxime
(produced by the reaction of the ketone with hydroxylamine - in the
form of the salt, hydroxylamine hydrogensulfate):
 Fertilizer

 The main disadvantages are (1) separation of the product being too difficult and
(2) corrosion of reactors by using concentrated acids as catalysts.
 polymerization of Nylon 6
 It is possible to polymerize by condensation a single monomer with
two opposing groups at its ends.
 Nylon 6 is the linear addition polymer of caprolactam (6-amino-

caproic acid).
 The three main reversible reaction steps in nylon 6 production.

hydrolysis, polycondensation, and polyaddition

 Hydrolysis reaction
 Is used to open the caprolactam ring, forming ε-aminocaproic acid:

• This reaction proceeds in molten caprolactam in the prescence of small weight

percent water.

• A material such as phosphoric acid is added at low concentration to act as a

chain stabliser and help achieve the desired final viscosity(MW)
Ring opening mechanisms

Hydrogen transfer

Electron rearrangement

Nucleophilic attack
 Polyaddition
 Mainly responsible for the growth of the linear polymer chains.
 It is the most important reaction as soon as certain amount of end
groups has been made available by the hydrolysis of caprolactam.
 Cont…

• The polymers dissolves in the unreacted caprolactam.

• The polymer end groups affect the stablity and final MW of the
polyamide.
• Organic acid (acetic acid) can be added as chain stablisers
 The first equilibrium reaction suggests that we must use high water
concentrations in order to convert as much caprolactam as possible
into aminocaproic acid.
 We may think of aminocaproic acid as a polymer molecule of DP one.
 Polycondensation reaction

 To further increase its MW.

 The forward reaction proceeds when an amine end group performs a
nucleophilic attack on a carboxyl end group to form an amide group.
 The reverse reaction involves the nucleophilic attack of water on the
amide functionality.
The Flow Chart

H2O VAPORS
ACETIC ACID WATER
N2

CAPROLACTAM CL, acetic acid,

CL MELTER
[CL] water, TiO2 POLYMERIZATIO
N
CHIPS RIBBON

CENTRIFU WASHER CUTTE WATER EXTRUDER

GE R BATH

Water Washings WATER

DRYE
R
SPINNING
Recovered Monomer
RECOVERY
Nylon 6,6 Polymer Production
 Cont..
 As with other polyamides, the classical route for the synthesis of nylon
6,6 is the direct reaction between a dicarboxylic acid (adipic acid) and
a diamine (hexamethylenediamine).
 In practice, however, to achieve an exact stoichiometric equivalence
between the functional groups, a 1:1 salt of the two reactants is
prepared initially and subsequently heated at a high temperature to
form the polyamide.
 Cont..
 The pressure is subsequently reduced to atmospheric pressure, and heating is
continued until completion of polymerization:
 Cont..
 For nylon6,6, an intermediate hexamethylene diammonium adipate salt is

formed.

 A slurry of 60 to 80% of the recrystallized salt is heated rapidly.

 The steam that is released is cleaned by air.

 Temperature is then raised to 220°C and finally to 270 to 280°C when the

monomer conversion is about 80 to 90% while maintaining the steam pressure

generated during polymerization at 200 to 250 psi.

 Cont..
 Since the polymerization reaction occurs above the melting points of both
reactants and the polymer, the polymerization process is known as melt
polymerization.
 Other polyamides of commercial importance are:
 Nylons 11
• The numerals in the trivial names refer to the number of carbon
 Nylon 12
atoms in the monomer(s).
 Nylon 6,10 and • The first number refers to the number of carbon atoms in the
diamine while the second number refers to the total number of
 Nylon6,12.
carbon atoms in the acid.
 Nomex & Kevlar
Polypropylene
 Cont..
 Polypropylene is the second most simple and second most widely used
synthetic polymer in the world.
 PP is one of the polyolefins, a family of polymers containing only
carbon and hydrogen. 
 Polypropylene is one of those rather versatile polymers out there.
 It serves double duty, both as a plastic and as a fiber.
 Cont..
 As a plastic it's used to make things like dishwasher-safe food
containers because it doesn't melt below 160oC, or 320oF.
 Cont..
 Structurally, it's a vinyl polymer, and is similar to polyethylene, only
that on every other carbon atom in the backbone chain has a methyl
group attached to it.
 Polypropylene can be made from the monomer propylene by 
Ziegler-Natta polymerization and by metallocene
catalysis polymerization.
 Cont..
 They are ordered polymers of a high degree of crystallinity.
 Polypropylene can be made with different tacticities.
 Most polypropylene we use is isotactic.
 This means that all the methyl groups are on the same side of the
chain, like this:
 Cont..
 But sometimes we use atactic polypropylene. 
 Atactic means that the methyl groups are placed randomly on both
sides of the chain like this:
 Cont..
 Ziegler–Natta-type catalysts are used to produce stereoregular
polypropylene.
 Usually 90% or more of the polymer is in the isotactic form.
 Isotactic polypropylene is essentially linear, with an ordered
arrangement of propylene molecules in the polymer chain.
 For the isotactic form, because of the size of the pendant [–CH3] group
the backbone can no longer exist in the planar zigzag form; it must
rotate.
Acrylic polymer
production
 Introduction
 Acrylics are synthetic polymers made from a monomer called
acrylonitrile with an average molecular weight of ~100,000, about
1900 monomer units.
 For a fiber to be called "acrylic“ in the US, the polymer must contain at
least 85% acrylonitrile monomer.
 Typical comonomers are vinyl acetate or methyl acrylate.
 Acrylic fibres are third largest class of synthetic fibre after polyester
and nylons.
 Introduction
 Acrylonitrile is obtained by reacting propylene with ammonia:

 Another important monomer, methylmethacrylate (acrylic), is obtained

by reacting propylene with carbon monoxide, oxygen and methanol:
 Cont’d
 Polyacrylonitrile is a vinyl polymer, and a derivative of the acrylate
family of polymers.
 It is made from the monomer acrylonitrile by suspension methods using
free radical vinyl polymerization.
Acrylonitrile
 Cont’d

 A member of the important family of acrylic resins, it is a hard, rigid

thermoplastic material that is resistant to most solvents and chemicals,

slow to burn, and of low permeability to gases.

 Most polyacrylonitrile is produced as acrylic and modacrylic fibre, a

common substitute for wool in clothing and home furnishings.

 Cont’d

 Because PAN is difficult to dissolve in organic solvents and is highly

resistant to dyeing, very little fibre is produced containing PAN alone.

 On the other hand, a copolymer containing PAN and 2 to 7 percent of

a vinyl comonomer such as vinyl acetate can be readily spun to fibres

that are soft enough to allow penetration by dyestuffs

Cont’d
Thank you!